Synthesis and transformations of metallacycles. 31. Catalysts based on cobalt complexes in reactions of trialkyl- and alkylhaloalanes with olefins, allenes, and acetylenes

Ибрагимов, А. Г.; Khafizova, L. O.; …, Academy of Sciences of the Bashkortostan Republic and Ufa Scientific Center of the Russian Academy; Yakupova, L. R.; Borisova, A. L.; Джемилев, У. М.

doi:10.1023/b:rucb.0000012366.05437.af

Cited by 6 publications

(5 citation statements)

References 2 publications

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“…This procedure has already been used by Ibragimov et al to provide evidence for the formation of aluminometallacycles in reactions involving alkynes and diethylaluminum chloride [31].…”

Section: Discussionmentioning

confidence: 99%

In SituGeneration of Molybdenum-Based Catalyst for Alkyne Metathesis: Further Developments and Mechanistic Insights

Lopez

Zaranek

Pawluć

et al. 2016

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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-Molybdenum-based catalysts are among the best candidates to achieve alkyne metathesis. They can be either well-defined carbynes, previously synthesized before their use, but also prepared in situ upon using stable molybdenum carbonyl complexes, or high oxidation state molybdenum salts that need a previous alkylation, both type of precursors being "activated" by hydroxyl-containing compounds such as phenols and silanols. This paper is presenting studies made on these systems, directed towards the knowledge of the reaction paths leading to the active species, and in particular to define the essential role of hydroxyl-containing co-catalyst in the formation of the active species, still ill-defined. From an analysis of the byproducts formed during the reaction, as well as of the initial products, reaction paths to access catalytic carbyne species is suggested, where the ligand environment consists of phenoxy (or siloxy) groups, typically required and identified to lead to alkyne metathesis in the case of well-defined catalysts.Résumé -Génération in situ de catalyseurs de métathèse des alcynes à base de molybdène : développements récents et approche mécanistique -Les catalyseurs à base de molybdène font partie des candidats les plus efficaces pour la métathèse des alcynes. Ceux-ci peuvent être soit des carbynes de molybdène préalablement synthétisés avant leur mise en oeuvre, mais aussi préparés in situ via l'entremise de complexes à base de molybdène carbonyles, ou encore par alkylation de sels à haut degré d'oxydation, ces deux types de précurseurs nécessitant la présence de composés hydroxylés tels que des phénols ou silanols. Cette publication a pour objet de présenter des études visant à déterminer le mode de formation des espèces catalytiques impliquées dans ces deux systèmes, et en particulier du rôle du cocatalyseur hydroxylé, encore mal défini, dans la formation des espèces actives. De l'analyse des produits secondaires obtenus en cours de réaction, ainsi que des produits initiaux, on propose des voies de formation des espèces catalytiques de type carbyne, dont la particularité serait de disposer d'un environnement de ligands de type phénoxy (ou silyloxy), typiquement requis et identifiés pour favoriser le cycle catalytique relatif à la métathèse des alcynes sur des complexes carbynes bien définis.

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“…This procedure has already been used by Ibragimov et al to provide evidence for the formation of aluminometallacycles in reactions involving alkynes and diethylaluminum chloride [31].…”

Section: Discussionmentioning

confidence: 99%

In SituGeneration of Molybdenum-Based Catalyst for Alkyne Metathesis: Further Developments and Mechanistic Insights

Lopez

Zaranek

Pawluć

et al. 2016

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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“…The solvent-coordinated product was subjected to ligand exchange using DMAP, and the DMAP-coordinated aluminum complex structure was also confirmed by NMR. Because of the high activity of the trialkylaluminum reagent, we further confirmed the yield and regioselectivity of the reaction by reacting it with the degassed D 2 O solution of DCl to generate deuterated product …”

mentioning

confidence: 87%

“…Because of the high activity of the trialkylaluminum reagent, we further confirmed the yield and regioselectivity of the reaction by reacting it with the degassed D 2 O solution of DCl to generate deuterated product. 22 We next systematically evaluated other reaction conditions. When DIBAL-H was replaced by other aluminum reagents, such as Red-Al, LiAlH 4 , HAlCl 2 •2THF, AlEt 3 , Al( i Bu) 3 , AlEt 2 Cl, and Al( i Bu) 2 Cl, poor results were given (Table S1).…”

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confidence: 99%

Iron-Catalyzed Alkene Hydroalumination

Zhang

et al. 2023

Org. Lett.

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Hydroalumination of olefins generally gives thermodynamically controlled anti-Markovnikov addition selectivity in literatures. In this paper, a highly Markovnikov hydroalumination of aromatic terminal alkenes was realized to prepare various new benzylaluminum complexes by using the well-defined 2,9-diaryl-1,10-phenanthroline modified iron complex as the catalyst and commercially available DIBAL-H as the aluminum hydride reagent. This is the first ironcatalyzed alkene hydroalumination, and the regioselectivity observed in this study is different from the related reactions reported in the literatures.

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“…A few years later, Khafizova et al reported a similar approach catalyzed by the cobalt phosphine complexes [Co] (CoCl 2 :Ph 3 P = 1:2) (Scheme b) . The reaction of styrene with EtAlCl 2 , Mg, and 10 mol % [Co] in THF at 20 °C for 8–10 h yielded the heterocyclic AlC 2 -2a and the acyclic byproduct 2-1 in a 1:3 ratio in 70% overall yield.…”

Section: Al1e2 Systemsmentioning

confidence: 99%

“…A few years later, Khafizova et al reported a similar approach catalyzed by the cobalt phosphine complexes [Co] (CoCl 2 :Ph 3 P = 1:2) (Scheme 2b). 32 The reaction of styrene The metal-catalyzed AlC 2 ring formation is not limited to aluminacyclopropanes but is applicable to construct aluminacyclopropenes (Scheme 2c). 33 Dzhemilev et al reported that cycloalumination of 1,2-diphenylacetylene and oct-4-yne with EtAlCl 2 catalyzed by Cp 2 TiCl 2 in THF at 20 °C for 8−10 h gave AlC 2 -3 and AlC 2 -4 in 90% and 65% yields, respectively.…”

Section: Al 1 E 2 Systemsmentioning

confidence: 99%

Three-Membered Aluminacycles

Yan

Kinjo

2023

J. Am. Chem. Soc.

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Three-membered-ring scaffolds of carbocycles, namely, cyclopropanes and cyclopropenes, are ubiquitous in natural products and pharmaceutical molecules. These molecules exhibit a peculiar reactivity, and their applications as synthetic intermediates and versatile building blocks in organic synthesis have been extensively studied over the past century. The incorporation of heteroatoms into three-membered cyclic structures has attracted significant attention, reflecting fundamental differences in their electronic/geometric structures and reactivities compared to their carbon congeners and their associated potential for exploitation in applications. Recently, the chemistry of low-valent aluminum species, alumylenes, dialumenes, and aluminyl anions, has dramatically developed, which has allowed access to hitherto unprecedented aluminacycles. This Perspective focuses upon advances in the chemistry of three-membered aluminacycles, including their synthetic protocols, spectroscopic and structural properties, and reactivity toward various substrates and small molecules.

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Synthesis and transformations of metallacycles. 31. Catalysts based on cobalt complexes in reactions of trialkyl- and alkylhaloalanes with olefins, allenes, and acetylenes

Cited by 6 publications

References 2 publications

In SituGeneration of Molybdenum-Based Catalyst for Alkyne Metathesis: Further Developments and Mechanistic Insights

In SituGeneration of Molybdenum-Based Catalyst for Alkyne Metathesis: Further Developments and Mechanistic Insights

Iron-Catalyzed Alkene Hydroalumination

Three-Membered Aluminacycles

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